Atomistic chemical computation of Olefin polymerization reaction catalyzed by (pyridylamido)hafnium(IV) complex: Application of Red Moon simulation

We have realized the microscopic simulation of olefin polymerization, that is, the simulation of the catalytic polymerization (CP) reaction system composed of (pyridylamido)hafnium(IV) complex as the catalyst. For this purpose, we adopted Red Moon (RM) method, a novel molecular simulation method to simulate the complex reaction system. First, according to the previous research, with the help of the QM calculation, we proposed a model system and elementary processes and explained the theoretical treatment of the simulation by the RM method (the RM simulation). In addition, we also proposed a macroscopic simulation based on chemical kinetics simulation. Then, we performed two simulations and compared them in terms of the effective time evolution of the three macroscopic physical quantities, the number-average molecular weight M_n , the mass-average molecular weight M_w , and the molar-mass dispersity Đ_M . The comparison showed that the two simulations are in quantitative or partially qualitative agreement with each other. Therefore, it is concluded that the RM simulation could not only simulate the CP reaction process microscopically, but also it is connected essentially to reproduce the time evolution of the macroscopic physical quantities on the basis of its microscopic simulation data. © 2018 Wiley Periodicals, Inc.     

In situ observation of formation of misfit dislocations in pseudomorphic monolayer overgrowth of metals and non-metals

Epitaxial overgrowth in cases of deposit and substrate combinations of PbSe/PbS, Au/Pd and Pd/Au were observed in situ in an electron microscope. It was found that the growth proceeds with the very characteristic features of monolayer overgrowth as implied by the theory of Frank and Van der Merwe; no indication of nucleation was observed and the formation of misfit dislocations was noticed over the whole area of films at certain critical thicknesses of the overgrowths. Points were noted which distinguish the monolayer overgrowth from the case where misfit dislocations are introduced in nucleated islands, to which Matthews has counted the growth processes in these combinations. The importance of climb motion as well as slip motion was stressed as the mechanism of introduction of misfit dislocations. Some results of electron diffraction and electron microscopy of films prepared in separate evaporation units were also quoted. These were to examine the relation between misfit dislocation density and mean lattice parameter and the effect of degree of vacuum on the growth mode and to indicate that the same growth mode takes place for some other combinations of IV–VI compounds, SnTe/PbSe, PbTe/PbS and PbTe/PbSe.     

Synthesis of chitosan resin possessing a phenylarsonic acid moiety for collection/concentration of uranium and its determination by ICP-AES

A chitosan resin possessing a phenylarsonic acid moiety (phenylarsonic acid type chitosan resin) was developed for the collection and concentration of trace uranium prior to inductively coupled plasma (ICP) atomic emission spectrometry (AES) measurement. The adsorption behavior of 52 elements was systematically examined by packing it in a minicolumn and measuring the elements in the effluent by ICP mass spectrometry. The resin could adsorb several cationic species by a chelating mechanism, and several oxo acids, such as Ti(IV), V(V), Mo(VI), and W(VI), by an anion-exchange mechanism and/or a chelating mechanism. Especially, U(VI) could be adsorbed almost 100% over a wide pH region from pH 4 to 8. Uranium adsorbed was easily eluted with 1 M nitric acid (10 mL), and the 25-fold preconcentration of uranium was achieved by using a proposed column procedure, which could be applied to the determination of trace uranium in seawater by ICP-AES. The limit of detection was 0.1 ng mL⁻¹ for measurement by ICP-AES coupled with 25-fold column preconcentration.     

Surface treatment of PET fiber by EB-irradiation-induced graft polymerization and its effect on adhesion in natural rubber matrix

Aiming to develop a high performance fiber-reinforced natural rubber (NR) without using resorcinol formaldehyde latex (RFL) adhesives of environmental load substances, a special technique using electron beam (EB) irradiation-induced graft polymerization was applied to high-modulus polyethylene terephthalate (PET) fibers. Although PET is chemically inert, acrylate functional silane could be graft-polymerized onto the PET fiber surface by this special technique. The composite of NR and grafted PET fibers indicated a linear increase in the initial modulus with the fiber content. The fiber reinforced rubber with a good performance was obtained in the system of NR and grafted PET fibers.     

Ring-polymer Molecular Dynamics Simulation for the Adsorption of H2 on Ice Clusters (H2O)n (n=8, 10, and 12)

In the interstellar medium, the H₂ adsorption and desorption on the solid water ice are crucial for chemical and physical processes. We have recently investigated the probabilities of H₂ sticking on the (H₂O)₈ ice, which has quadrilateral surfaces. We have extended the previous work using classical MD and ring-polymer molecular dynamics (RPMD) simulations to the larger ice clusters, (H₂O)₁₀ and (H₂O)₁₂, which have pentagonal and hexagonal surfaces, respectively. The H₂ sticking probabilities decreased as the temperature increased for both cluster cases, whereas the cluster-size-independent profiles were observed. It is thought that the size independence of the probabilities is qualitatively understood from the similar binding energies for all the three cluster systems. Furthermore, the RPMD sticking probabilities are smaller than the classical ones because of the reduction in the binding energies owing to nuclear quantum effects, such as vibrational quantization.     

Flow-injection determination of total organic fluorine with off-line defluorination reaction on a solid sorbent bed

Considering recent reports on widespread occurrence and concerns about perfluoroalkyl substances (PFAS) in environmental and biological systems, analysis of these compounds have gained much attention in recent years. Majority of analyte-specific methods are based on a LC/MS/MS or a GC/MS detection, however many environmental or biological studies would benefit from a total organic fluorine (TOF) determination. Presented work was aimed at developing a method for TOF determination. TOF is determined as an amount of inorganic fluoride obtained after defluorination reaction conducted off-line using sodium biphenyl reagent directly on the sorbent without elution of retained analytes. Recovered fluoride was analyzed using flow-injection system with either fluorimetric or potentiometric detection. The TOF method was tested using perfluorocarboxylic acids (PFCA), including perfluorooctanoic acid (PFOA), as model compounds. Considering low concentrations of PFAS in natural samples, solid-phase extraction as a preconcentration procedure was evaluated. Several carbon-based sorbents were tested, namely multi-wall carbon nanotubes, carbon nanofibres and activated carbon. Good sorption of all analytes was achieved and defluorination reaction was possible to carry out directly on a sorbent bed. Recoveries obtained for PFCAs, adsorbed on an activated carbon sorbent, and measured as TOF, were 99.5 ± 1.7, 110 ± 9.4, 95 ± 26, 120 ± 32, 110 ± 12 for C4, C6, C8, C10 and C12-PFCA, respectively. Two flow systems that would enable the defluorination reaction and fluoride determination in a single system were designed and tested.     

Equilibrium analysis of reactions between aromatic anions and nonionic surfactant micelles by capillary zone electrophoresis.

Separability of some positional isomers of aromatic anions by capillary zone electrophoresis was improved by adding nonionic surfactants to a migrating solution. Eleven kinds of aromatic anions, including positional isomers, were used as analytes, and Brij-35, Brij-58 and Brij-78 were investigated as nonionic surfactants to form micelles, where hydrophobicities are different from each other. Increasing the concentration of the surfactants developed the separability of the anionic isomers. The interaction between the anions and the nonionic surfactant micelles is also investigated through the change in the electrophoretic mobility, and the binding constants are determined. Apparent electrophoretic mobility of the anions decreased with increasing concentrations of the nonionic surfactants. The decrease in the mobility, as well as the binding constant, was larger in the monovalent anions than in the divalent anions, which indicates that the interaction or reactivity of the monovalent analytes is higher than that of the divalent analytes. The reactivity of each anion was almost identical even when the kinds of the surfactants were changed, suggesting that the hydrophobicity of the polyoxyethylene group in the surfactant would have the main role for binding the analytes. The reactivity tendency among the positional isomers was almost similar to that in ion association-capillary zone electrophoresis using tertabutylammonium ion as a pairing ion. The results obtained in this work suggest that the anions are bound to the micelles by the hydrophobic interaction between analyte anions and the polyoxyethylene moiety of the surfactant micelles. Changes in the fluorescence intensity of the anions were also investigated; the results can explain well the mobility changes of the analytes.     

Application of a tie molecule model to the postyielding deformation of crystalline polymers

Our past paper reported that the postyielding deformation of crystalline polymers such as polyethylene (PE), poly(oxymethylene) (POM), poly(propylene) (PP) and nylon 6 (Ny 6) was expressed by master curves with a characteristic constant for each polymer when normalized true stress and true strain are plotted in both logarithmic graphs and suitably shifted. For a molecular understanding of the postyielding process, we present a tie molecule model which assumes that the tie molecules are pulled out from the lamellar fragment at a constant number of tie molecules. The limit in applicability of the model is in the final stage of fiber formation. Fundamental equations of the model are solved to give a critical point at which all the molecular parameters can be uniquely determined from the characteristic constant for each polymer. At the critical point, the tie molecule length monotonously increases at a fixed number of tie molecules. The limit of the tie molecule length increases in the order of PE, POM, PP and Ny 6. By using an empirical relationship between the area fraction of tie molecules and the degree of crystallinity of these polymers, it is found that the order of area fraction of the tie molecules in Ny 6, PP, POM and PE is entirely reversed to the order of weight fraction of the tie molecules of the above polymers.     

Analysis of complex formation between crown ethers and potassium ion by determining retention factors in reversed-phase high-performance liquid chromatography.

Retention factors in reversed-phase high-performance liquid chromatography (RP-HPLC) were utilized for the analysis of complex formation reaction of four crown ethers with potassium ion in water-methanol media. The crown ethers were injected as analytes, potassium ion was present in the eluent, and three types of reversed-phase columns were used. The retention factor of the crown ethers decreased with increasing concentrations of potassium ion in the eluent, which is attributed to the change in the species of the crown ether from a neutral ligand to a positively charged complex. The complex formation constants were determined by analyzing the changes in the retention factor with a non-linear least-squares method.     

Ab initio molecular orbital study of potential energy surface for the H2NO(B1)→NO(Π)+H2 reaction

The mechanism of the H₂NO(²B₁)→NO(²Π)+H₂ reaction has been examined using ab initio molecular orbital methods. Ground-state and first-excited-state potential surfaces were plotted at the FOCI/cc-pVTZ level of theory as functions of two appropriate internal degrees of freedom. A conical intersection was found on the C_s pathway that is symmetric with respect to the plane perpendicular to the molecular plane of C_2v H₂NO(²B₁). It is therefore considered that trajectories that start from H₂NO(²B₁) towards the product region detour around the conical intersection, pass through the neighborhood of the transition state that is located at the saddle point on the C_s pathway, and finally reach the products, NO(²Π)+H₂. Thus we can explain the mechanism of the H₂NO(²B₁)→NO(²Π)+H₂ reaction, which has remained unclear to date.